CN112125809B - Method for continuously preparing pentanediamine by decarboxylation of lysine - Google Patents
Method for continuously preparing pentanediamine by decarboxylation of lysine Download PDFInfo
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- CN112125809B CN112125809B CN202011095260.3A CN202011095260A CN112125809B CN 112125809 B CN112125809 B CN 112125809B CN 202011095260 A CN202011095260 A CN 202011095260A CN 112125809 B CN112125809 B CN 112125809B
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004472 Lysine Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006114 decarboxylation reaction Methods 0.000 title claims abstract description 29
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 21
- 229960003646 lysine Drugs 0.000 claims description 44
- 239000002994 raw material Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003930 superacid Substances 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- XAHQYEAIJGTPET-JEDNCBNOSA-N [(1s)-5-amino-1-carboxypentyl]azanium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.NCCCC[C@H]([NH3+])C(O)=O XAHQYEAIJGTPET-JEDNCBNOSA-N 0.000 claims description 3
- RRNJROHIFSLGRA-JEDNCBNOSA-N acetic acid;(2s)-2,6-diaminohexanoic acid Chemical compound CC(O)=O.NCCCC[C@H](N)C(O)=O RRNJROHIFSLGRA-JEDNCBNOSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229960005357 lysine acetate Drugs 0.000 claims description 3
- 229960005337 lysine hydrochloride Drugs 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910006406 SnO 2 At Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920006118 nylon 56 Polymers 0.000 description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 108010048581 Lysine decarboxylase Proteins 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920006309 Invista Polymers 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for continuously preparing pentanediamine by decarboxylation of lysine. The method adopts the solid super acidic catalyst as a carrier, provides an acidic environment required by lysine decarboxylation, effectively avoids the use of liquid acid, solves the problem of equipment corrosion, and has yield equivalent to that of the liquid acid; meanwhile, the method is carried out on a continuous reactor, has high reaction activity, no corrosion, easy continuous large-scale production and very wide industrial application prospect.
Description
Technical Field
The invention relates to the field of synthesis of pentanediamine, and particularly relates to a method for continuously preparing pentanediamine by decarboxylation of lysine.
Background
The nylon 56 material can be produced by polymerizing 1, 5-pentanediamine, which is also called cadaverine, and adipic acid. The nylon 56 material has good comprehensive properties, such as high moisture absorption and sweat releasing rate, good air permeability, good softness and dyeing property, and the like, is wear-resistant, chemical-resistant, good in flame retardance, easy to process, and has strong competitive advantages in nylon material series. The upstream raw material adiponitrile of nylon 66 is monopolized by foreign companies (Invista, rohidia and the like) and becomes a calorie neck technology which restricts the rapid development of the nylon industry in China. Nylon 56 has excellent properties comparable to nylon 66 and is a substitute material for the latter. Since the production process and market of adipic acid are well-established, and the adipic acid is mostly prepared by oxidation of KA oil or hydrogenation of benzene, while the production of the raw material pentanediamine is not mature at present and a large number of commercial products are not sold so far, the development of a new method for synthesizing 1, 5-pentanediamine is the core of the production of nylon 56.
The most reported production method of 1, 5-pentanediamine is a biological fermentation method. The Nanjing industry university utilizes bean dreg hydrolysate to ferment and produce pentanediamine (CN201810954086. X), but the pentanediamine has toxicity to microorganisms and influences the production efficiency. A plurality of pentanediamine biological fermentation method patents (CN 201811506539.9, CN201710453415.8, CN201710011198.7 and the like) are applied by Shanghai Kaiser Biotechnology research and development center, and the patent contents indicate that the problem of toxicity of pentanediamine to strains is effectively solved by inoculating a seed solution of a lysine decarboxylase strain in a lysine fermentation process. However, the biological fermentation method still has great difficulties, such as low lysine decarboxylase activity, poor toxicity resistance, low product concentration, excessive separation cost and the like.
Compared with a biological fermentation decarboxylation method, the chemical decarboxylation method has obvious advantages, such as high catalyst activity, easy product separation and the like. However, the current chemical method research is only focused on a kettle type batch reactor, the requirement of industrial continuous production cannot be met, and meanwhile, good pentamethylenediamine yield (ACS Catalysis, 2016, 6, 7303-7310; ACS sustamable Chemistry & Engineering, 2017, 5, 3290-3295) can be obtained only by adjusting the pH of a solution to be strongly acidic with a strong liquid acid, and the problem of equipment corrosion is serious. The solid super acid refers to an acid which is more acidic than 100% sulfuric acid, for example, the acid strength is represented by a Hammett acidity function H, the H value of 100% sulfuric acid is-11.9, and the solid acid with the acid strength less than-11.9 is called the solid super acid. The solid super acid has wide application in catalytic reaction, such as hydrocarbon cracking, reforming and other reactions catalyzed by acid, and is the basis of a series of important industries.
Disclosure of Invention
The invention provides a method for continuously preparing pentanediamine by decarboxylation of lysine, which solves the problems that equipment is easy to corrode and continuous preparation cannot be realized due to the utilization of liquid acid in the prior art.
The technical scheme for realizing the invention is as follows:
a method for continuously preparing pentanediamine by decarboxylation of lysine comprises the steps of placing a solid super acidic catalyst in a continuous reactor, and introducing lysine or lysine salt aqueous solution for continuous decarboxylation reaction to prepare a product containing the pentanediamine.
The continuous reactor comprises a fixed bed reactor and a moving bed reactor, and lysine or lysine salt aqueous solution enters the continuous reactor through a high-pressure pump to contact with the solid super acid catalyst.
The concentration of the lysine or lysine salt water solution is 0.001 to 3M, and the mass space velocity of the raw material is 0.05 to 10.0 h -1 The reaction temperature is 150 to 400 ℃, the reaction pressure is 0.2 to 15.0 Mpa, and the reaction atmosphere is N 2 、He、Ar、CH 4 、C 2 H 6 、H 2 CO or CO 2 Any one or more of them.
The solid super acidic catalyst is a supported catalyst and comprises a super acidic carrier and a reaction active center.
The super acid carrier is at least one of sulfate radical promoting oxide or composite oxide.
The sulfate radical promoting oxide is SO 4 2- /ZrO 2 、SO 4 2- /TiO 2 、SO 4 2- /Fe 2 O 3 、SO 4 2- /SiO 2 、SO 4 2- /Al 2 O 3 、SO 4 2- /SnO 2 、SO 4 2- /ZrO 2 -NiO、SO 4 2- /ZrO 2 -SiO 2 、SO 4 2- /ZrO 2 -V 2 O 5 、SO 4 2- /ZrO 2 -SnO 2 At least one of (1).
The composite oxide is WO 3 /ZrO 2 Or MoO 3 /ZrO 2 。
The reaction active center is at least one of Pd, pt, cr, pb, co, cd, fe, cu, ru and Nb, and the mass fraction of the reaction active center in the solid super acidic catalyst is 0.1 to 50%.
The lysine salt is any one or combination of any several of lysine hydrochloride, lysine sulfate, lysine acetate and lysine phosphate.
The invention has the beneficial effects that: the method adopts the solid super acidic catalyst as a carrier, provides an acidic environment required by lysine decarboxylation, effectively avoids the use of liquid acid, solves the problem of equipment corrosion, and has yield equivalent to that of the liquid acid; meanwhile, the method is carried out on a continuous reactor, has high reaction activity, no corrosion, easy continuous large-scale production and very wide industrial application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The analytical methods and conditions in the examples of the present application are as follows:
the starting materials and the products were analyzed by Waters liquid chromatography using a C18 reverse phase column from Waters.
According to an embodiment of the application, a fixed bed reactor is selected, and the mass airspeed of the raw materials is 0.3 to 2.0 h -1 The reaction temperature is 200 to 400 ℃, the reaction pressure is 0.2 to 5.0 Mpa, and the raw materials enter a reactor through a high-pressure pump.
Lysine conversion = [ (moles of lysine in feed) - (moles of lysine in discharge) ]/(moles of lysine in feed) × (100%).
Pentanediamine yield = (moles of pentanediamine in the discharge) ÷ (moles of lysine in the feed) × (100%).
1. Catalyst preparation
1.1 SO 4 2- -ZrO 2 Preparation of solid super acidic carrier
And (3) preparing a zirconium hydroxide precursor.
Weighing a certain amount of zirconium oxychloride octahydrate solid, dissolving the zirconium oxychloride octahydrate solid in deionized water, and fully stirring the solution at a constant speed until the solution is clear to obtain a 0.4 mol/L zirconium oxychloride aqueous solution. Concentrated ammonia water is added dropwise under stirring until a thick suspension state is formed. When the pH =9, the dropwise addition of concentrated ammonia water was stopped and stirring was continued for 15 min. After standing for 24 h, filtering and washing, and removing water in an oven at 120 ℃ for 12 h.
SO 4 2- -ZrO 2 And (3) preparing a solid superacid carrier.
Fully grinding the zirconium hydroxide precursor to powder, and soaking the zirconium hydroxide precursor into 1 mol/L sulfuric acid solution, wherein the solid-to-liquid ratio is 1: and 5, soaking for 2 h. And (4) removing the redundant sulfuric acid by suction filtration, and removing water from the filter cake in a 120 ℃ oven for 12 hours. Baking in a muffle furnace after drying, wherein the baking condition is 650 ℃, the baking time is 3 h, and the heating rate is 5 ℃/min. The powder after roasting is a solid super acidic carrier. And respectively preparing 20 to 40 meshes of No. 1 catalyst by extrusion.
1.2 WO 3 -ZrO 2 Preparation of solid super acidic carrier
Preparation of WO by coprecipitation 3 -ZrO 2 And (3) a carrier. The ammonium metatungstate aqueous solution with certain concentration and the ammonia water mixed solution are strongly stirred, the zirconium oxychloride aqueous solution is slowly added under the stirring condition, and the atomic ratio of W to Zr is controlled. Adding ammonia water to make the pH value of the final solution reach about 10, emulsifying the suspension at high speed for 5 min, filtering and washing, and drying the filter cake. After 3 h of high-temperature roasting, WO is obtained 3 -ZrO 2 A solid super acidic carrier. And extruding to obtain the 20-40 mesh No. 2 catalyst.
1.3 Load type M/SO 4 2- -ZrO 2 Preparation of solid super acidic catalyst
Preparing Fe/SO with 5% loading capacity by adopting isovolumetric immersion method 4 2- -ZrO 2 A catalyst. The preparation process comprises the following steps: 1.1 g of ferric nitrate was weighed and dissolved in 10 mL of water to obtain a red color developing solution. To this solution was added 5 g SO 4 2- -ZrO 2 The carrier is evenly stirred, dried in an oven at 100 ℃ overnight and then calcined in a muffle furnace at 550 ℃ with the heating rate of 5 ℃/min, and a sample is obtained after 240 min of calcinationReducing at 350 ℃ in a hydrogen/argon atmosphere to obtain Fe/SO with 5 percent of load capacity 4 2- -ZrO 2 And extruding the catalyst to prepare a catalyst No. 3 with the mesh size of 20 to 40.
Cu/SO with 5% loading capacity is prepared by adopting an isovolumetric immersion method 4 2- -ZrO 2 Catalyst and Pd/SO with 5 percent of loading capacity 4 2- -ZrO 2 Catalyst and Pt/SO with 5% of loading capacity 4 2- -ZrO 2 Catalyst and Ru/SO with 5% of loading 4 2- -ZrO 2 The catalyst is extruded to obtain 20 to 40 mesh catalysts 4#, 5#, 6#, and 7#.
80 g of No. 4 catalyst, 20 g of pseudo-boehmite and 10% of dilute nitric acid are taken to be mixed uniformly and extruded into strips for molding, the mixture is roasted for 4 hours at 550 ℃, and the catalyst No. 8 with the mesh size of 20 to 40 is prepared by extrusion.
80 g of No. 4 catalyst, 28 g of pseudo-boehmite and 10% of dilute nitric acid are taken, are uniformly mixed, are extruded into strips and are molded, are roasted for 4 hours at 550 ℃, and are extruded to prepare the catalyst No. 9 with the mesh size of 20 to 40.
80 g of No. 4 catalyst, 50 g of pseudo-boehmite and 10% of dilute nitric acid are taken to be mixed uniformly and extruded into strips for molding, the mixture is roasted for 4 hours at 550 ℃, and the catalyst No. 10 with the mesh size of 20 to 40 is prepared by extrusion.
1.4 Load type M/WO 3 -ZrO 2 Catalyst and process for preparing same
Preparation of Fe/WO with 5% loading capacity by adopting equal-volume impregnation method 3 -ZrO 2 A catalyst. The preparation method comprises the following specific steps: 1.1 g of ferric nitrate was weighed and dissolved in 10 mL of water to obtain a red color developing solution. To this solution was added 5 g of WO 3 -ZrO 2 Uniformly stirring a carrier, drying in an oven at 100 ℃ overnight, calcining at 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min for 240 min to obtain a sample, and reducing at 350 ℃ in a hydrogen/argon atmosphere to obtain Fe/WO with the load of 5% 3 -ZrO 2 And extruding the catalyst to prepare a catalyst No. 11 with the mesh size of 20 to 40.
Fe/WO with the loading capacity of 1%, 10% and 20% is prepared by adopting an isovolumetric immersion method 3 -ZrO 2 And extruding the catalyst to obtain 20-40 mesh catalysts 12#, 13#, and 14#.
2. Synthesis example
Comparative Synthesis example
γ-Al 2 O 3 Is weak solid acid, takes the weak solid acid as a carrier, and prepares 5 percent Fe/gamma-Al by an impregnation method 2 O 3 The catalyst was prepared according to the same method as in catalyst preparation example 1.3. Mixing 5% Fe/gamma-Al 2 O 3 The catalyst is loaded in a fixed bed reactor after being granulated, and the catalyst is preactivated under the condition of N 2 The flow rate is 30 mL/min, the temperature is increased to 500 ℃ at the speed of 2 ℃/min, the temperature is kept at 500 ℃ for 1 hour, then the temperature is reduced to the required reaction temperature of 200 ℃ under the nitrogen atmosphere, the pressure of the reaction system is increased to 3 MPa by using hydrogen, and the mass space velocity of the lysine water solution is 0.3 h -1 Under these conditions, the yield of pentamethylenediamine was 5.2%.
2.1 Lysine decarboxylation on different superacid catalysts
Filling the catalyst No. 1-14 solid super acidic catalyst in a fixed bed reactor, and pre-activating the catalyst under the condition of N 2 The flow rate is 30 ml/min, the temperature is increased to 500 ℃ at the speed of 2 ℃/min, the temperature is kept at 500 ℃ for 1 hour, then the temperature is reduced to the required reaction temperature of 200 ℃ under the nitrogen atmosphere, the pressure of the reaction system is increased to 3 MPa by using hydrogen, and the mass space velocity of the lysine water solution is 0.3 h -1 The reaction results under these conditions are shown in Table 1.
TABLE 1 evaluation results of a catalyst for continuous preparation of pentamethylenediamine by decarboxylation of lysine
2.2 Lysine decarboxylation reaction results at different reaction temperatures
0.5 g of No. 5 catalyst is loaded into a fixed bed reactor with the inner diameter of 8 mm, the temperature is increased to 500 ℃ at the rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to the required reaction temperature under the nitrogen atmosphere, and the pressure of a reaction system is increased to 3 MPa by using hydrogen. Introducing lysine water solution into a reactor from top to bottom, wherein the mass space velocity of the raw material is 0.3 h -1 Different reaction temperaturesThe reaction results in degrees are shown in Table 2.
TABLE 2 evaluation results of lysine decarboxylation reaction at different reaction temperatures
2.3 Lysine decarboxylation reaction results under different reaction pressures
0.5 g of No. 5 catalyst is loaded into a fixed bed reactor with the inner diameter of 8 mm, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is reduced to 200 ℃ under the nitrogen atmosphere, and the pressure of a reaction system is increased to the pressure required by the reaction by hydrogen. Introducing lysine aqueous solution into a reactor from top to bottom, wherein the mass space velocity of the raw material is 0.3 h -1 The results of the lysine decarboxylation reaction at different reaction pressures are shown in Table 3.
TABLE 3 results of lysine decarboxylation reaction at different reaction pressures
2.4 Reaction results of different lysine salt species on solid super acidic catalyst
0.5 g of No. 5 catalyst is loaded into a fixed bed reactor with the inner diameter of 8 mm, the temperature is raised to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, the temperature is kept for 1 hour, then the temperature is lowered to 200 ℃ under the nitrogen atmosphere, and the pressure of a reaction system is raised to 3 MPa required by the reaction by using hydrogen. Introducing lysine water solution raw materials into a reactor from top to bottom, wherein the mass space velocity of the raw materials is 0.3 h -1 The solutes in the aqueous lysine solution were lysine hydrochloride, lysine sulfate, lysine acetate, and lysine phosphate, respectively, and the results of the lysine decarboxylation reaction are shown in table 4.
TABLE 4 Effect of different lysine salt types on solid superacid catalysts on reaction results
2.5 Lysine decarboxylation reaction result under different raw material mass airspeeds
Using a 5# catalyst, the reaction temperature is 200 ℃, and the mass space velocity of the lysine aqueous solution is 0.3 h -1 ，1.0 h -1 ，2.0 h -1 Otherwise, the reaction conditions were the same as in example 2.1, and the reaction results are shown in Table 5.
TABLE 5 lysine decarboxylation results at different mass airspeeds
2.6 Reaction results of different reactor types
The same procedure as in example 2.1 was repeated except that No. 6 catalyst was used, the reaction temperature was 200 ℃ and the reactors were a fluidized bed reactor and a moving bed reactor, respectively. The reaction results are shown in Table 6.
TABLE 6 results of lysine decarboxylation reaction at different reactor types
2.7 Reaction results under different reaction atmospheres
Using No. 10 catalyst, the reaction temperature is 200 ℃, and the reaction atmosphere is N 2 、H 2 CO, other conditions were the same as in example 2.1. The reaction results are shown in Table 7.
TABLE 7 results of lysine decarboxylation reaction under different reaction atmospheres
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The method for continuously preparing the pentanediamine by decarboxylation of the lysine is characterized by comprising the following steps: putting a solid super acidic catalyst into a continuous reactor, and introducing lysine or lysine salt aqueous solution to perform continuous decarboxylation reaction to prepare a product containing pentanediamine;
the concentration of the lysine or lysine salt aqueous solution is 0.001 to 3M, and the mass space velocity of the raw material is 0.05 to 10.0 h -1 The reaction temperature is 150 to 400 ℃, the pressure is 0.2 to 15.0 MPa, and the reaction atmosphere is N 2 、He、Ar、CH 4 、C 2 H 6 、H 2 CO or CO 2 Any one or more of them;
the solid super acidic catalyst is a supported catalyst and comprises a super acidic carrier and a reaction active center;
the super acid carrier is at least one of sulfate radical promoting oxide or composite oxide;
the reaction active center is at least one of Pd, pt, cr, pb, co, cd, fe, cu, ru and Nb, and the mass fraction of the reaction active center in the solid super acidic catalyst is 0.1 to 50%.
2. The method for continuously preparing pentanediamine by decarboxylation of lysine according to claim 1, wherein: the continuous reactor comprises a fixed bed reactor and a moving bed reactor, and lysine or lysine salt aqueous solution enters the continuous reactor through a high-pressure pump to contact with the solid super acid catalyst.
3. The method for continuously preparing pentanediamine by decarboxylation of lysine according to claim 1, wherein: the sulfate radical promoting oxide is SO 4 2- /ZrO 2 、SO 4 2- /TiO 2 、SO 4 2- /Fe 2 O 3 、SO 4 2- /SiO 2 、SO 4 2- /Al 2 O 3 、SO 4 2- /SnO 2 、SO 4 2- /ZrO 2 -NiO、SO 4 2- /ZrO 2 -SiO 2 、SO 4 2- /ZrO 2 -V 2 O 5 、SO 4 2- /ZrO 2 -SnO 2 At least one of (1).
4. The method for continuously preparing pentanediamine by decarboxylation of lysine according to claim 1, wherein: the composite oxide is WO 3 /ZrO 2 Or MoO 3 /ZrO 2 。
5. The method for continuously preparing pentanediamine by decarboxylation of lysine according to claim 1 or 2, wherein: the lysine salt is at least one of lysine hydrochloride, lysine sulfate, lysine acetate and lysine phosphate.
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